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Non‐3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media
Author(s) -
Xu YanTong,
Ye ZiMing,
Ye JiaWen,
Cao LiMing,
Huang RuiKang,
Wu JunXi,
Zhou DongDong,
Zhang XueFeng,
He ChunTing,
Zhang JiePeng,
Chen XiaoMing
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201809144
Subject(s) - overpotential , oxygen evolution , imidazolate , cobalt , zeolitic imidazolate framework , electrolyte , catalysis , materials science , metal , inorganic chemistry , chemical engineering , adsorption , chemistry , metal organic framework , electrode , electrochemistry , metallurgy , organic chemistry , engineering
Cobalt imidazolate frameworks are classical electrocatalysts for the oxygen evolution reaction (OER) but suffer from the relatively low activity. Here, a non‐3d metal modulation strategy is presented for enhancing the OER activity of cobalt imidazolate frameworks. Two isomorphous frameworks [Co 4 (MO 4 )(eim) 6 ] (M=Mo or W, Heim=2‐ethylimidazole) having Co(eim) 3 (MO 4 ) units and high water stabilities were designed and synthesized. In different neutral media, the Mo‐modulated framework coated on a glassy carbon electrode shows the best OER performances (1 mA cm −2 at an overpotential of 210 mV in CO 2 ‐saturated 0.5 m KHCO 3 electrolyte and 2/10/22 mA cm −2 at overpotential of 388/490/570 mV in phosphate buffer solution) among non‐precious metal catalysts and even outperforms RuO 2 . Spectroscopic measurements and computational simulations revealed that the non‐3d metals modulate the electronic structure of Co for optimum reactant/product adsorption and tailor the energy of rate‐determining step to a more moderate value.